Acid dyes, process for the production thereof and their use
Dyes of formula (1) a process for their production and their use are described.
1. A dye of formula (1)
wherein
R 1 , R 2 , R 3 and R 4 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO 3 M—whereby at least two of them are SO 3 M,
R 5 , R 6 , R 7 and R 8 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO 3 M or alkylureido,
R 9 and R 15 independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,
R 10 and R 16 independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, or arylthio,
or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkyl-ureido and phenylureido,
R 11 , R 12 , R 13 , R 14 , R 17 , R 18 , R 19 , R 20 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyakyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbarnoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalk yl-N-monoarylsulfamo-yl and SO 3 M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO 3 M,
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation,
the dyes of formula (1) have two to six sulfonic acid groups,
and
whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R 11 and R 12 , and R 13 and R 14 , respectively can be positioned ortho or para to R 9 , meaning that when the amino rest bearing the substituents R 11 and R 12 is positioned ortho to R 9 , the amino rest bearing the substituents R 13 and R 14 is positioned para to R 9 , and vice versa;
and
the same applies to the amino rests bearing the substituents R 17 and R 18 , and R 19 to R 20 , respectively that can be positioned ortho or para to R 15 , meaning that when the amino rest bearing the substituents R 17 and R 18 is positioned ortho to R 15 , the amino rest bearing the substituents R 19 to R 20 is positioned para to R 15 , and vice versa.
2. The dye according to claim 1 , having formula (1a)
wherein
R 1a , R 2a , R 3a and R 4a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO 3 M, whereby at least two of them are SO 3 M,
R 5a , R 6a , R 7a and R 8a independent of each other is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, halogen, trifluoromethyl, —SO 3 M or (C 1 -C 4 )-acylamino,
R 9a and R 15a independent of one another is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
R 10a and R 16a independent of each other is unsubstituted, linear or branched (C 1 -C 4 )-alkyl, unsubstiuted (C 5 -C 7 )-cycloalkyl or substituted (C 5 -C 7 )-cycloalkyl with one or more substituents,
R 11a , R 12a R 13a , R 14a , R 17a , R 18a , R 19a and R 20a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
3. The dye according to claim 2 , wherein R 1a , R 2a , R 3a and R 4a independent of each other is SO 3 M, hydrogen, alkyl, alkoxy or halogen—whereby at least two of them are SO 3 M,
R 5a , R 6a , R 7a and R 8a independent of each other is hydrogen, methyl, halogen, —SO 3 M or acetylamino,
R 9a and R 15a independent of each other is cyano or carbamoyl,
R 10a and R 16a is methyl,
R 11a , R 12a R 13a , R 14a , R 17a , R 18a , R 19a and R 20a independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyetlaoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, alkyl substituted by SO 3 M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.
4. The dye according to claim 1 , having formula (1b)
wherein
R 1b , R 2b , R 3b and R 4b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO 3 M, whereby at least two of them are SO 3 M,
R 5b , R 6b , R 7b and R 8b independent of each other is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, halogen, trifluoromethyl, —SO 3 M or (C 1 -C 4 )-acylamino,
R 9b and R 15b independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl,
R 10b and R 16b independent of each other is unsubstituted, linear or branched (C 1 -C 4 )-alkyl, unsubstiuted (C 5 -C 7 )-cycloalkyl or substituted (C 5 -C 7 )-cycloalkyl with one or more substituents,
R 11b , R 12b R 13b , R 14b , R 17b , R 18b , R 19b and R 20b independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
5. The dye according to claim 4 , wherein
R 3b and R 4b is SO 3 M,
R 1b and R 2b is hydrogen,
R 5b , R 6b , R 7b and R 8b independent of each other is hydrogen, methyl, halogen, —SO 3 M or acetylamino,
R 9b and R 15b independent of each other is cyano or carbamoyl,
R 10b and R 16b is methyl,
R 11b , R 12b R 13b , R 14b , R 17b , R 18b , R 19b and R 20b independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO 3 M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.
6. The dye according to claim 1 , having formula (1c)
wherein
R 1c , R 2c , R 3c and R 4c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO 3 M, whereby at least two of them are SO 3 M,
R 5c , R 6c , R 7c and R 8c independent of each other is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, halogen, trifluoromethyl, —SO 3 M or (C 1 -C 4 )-acylamino,
R 9c and R 15c independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
R 10c and R 16c independent of each other is unsubstituted, linear or branched (C 1 -C 4 )-alkyl, unsubstiuted (C 5 -C 7 )-cycloalkyl or substituted (C 5 -C 7 )-cycloalkyl with one or more substituents,
R 11c , R 12c R 13c , R 14c , R 17c , R 18c , R 19c and R 20c independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, amino alkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
7. The dye according to claim 6 , wherein
R 2c and R 4c is SO 3 M,
R 1c and R 2c is hydrogen,
R 5c , R 6c , R 7c and R 8c independent of each other is hydrogen, methyl, halogen, —SO 3 M or acetylamino,
R 9c and R 15c independent of each other is cyano or carbamoyl,
R 10c and R 16c is methyl,
R 11c , R 12c R 13c , R 14c , R 17c , R 18c , R 19c and R 20c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO 3 M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.
8. The dye according to claim 1 , having formula (1d)
wherein
R 1d , R 2d , R 3d and R 4d independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO 3 M whereby at least two of them are SO 3 M,
R 5d , R 6d , R 7d and R 8d independent of each other is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, halogen, trifluoromethyl, —SO 3 M or (C 1 -C 4 )-acylamino,
R 9d and R 15d independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl,
R 10d and R 16d independent of each other is unsubstituted, linear or branched (C 1 -C 4 )-alkyl, unsubstiuted (C 5 -C 7 )-cycloalkyl or substituted (C 5 -C 7 )-cycloalkyl with one or more substituents,
R 11d , R 12d R 14d , R 17d , R 18d , R 19d and R 20d independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO 3 M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
9. The dye according to claim 8 , wherein
R 1d and R 3d is SO 3 M,
R 2d and R 4d is hydrogen,
R 5d , R 6d , R 7d R 8d independent of each other is hydrogen, methyl, halogen, —SO 3 M or acetylamino,
R 9d and R 15d independent of each other is cyano or carbamoyl,
R 10d R 16d is methyl,
R 11d , R 12d R 13d , R 14d , R 17d , R 18d , R 19d and R 20d independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO 3 M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.
10. A process for the preparation of the dye according to claim 1 and mixtures thereof comprising the steps
a) diazotization of a compound of formula (2)
wherein R 1 to R 4 are defined as in claim 1 ,
b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4)
wherein R 5 to R 8 are defined as in claim 1 , to yield an intermediate of formula (5)
c) diazotization of the compound of formula (5),
d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof
wherein R 11 to R 20 are defined as in claim 1 .
11. A chemical composition comprising one or more dye(s) according to claim 1 .
12. A chemical composition consisting essentially of two or more dyes according to claim 1 .
13. An aqueous solution for dying comprising one or more dyes according to claim 1 .
14. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim 1 .
15. An ink for digital textile printing comprising the dye according to claim 1 .
16. A fiber and blend containing the fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) according to claim 1 either in chemically and/or physically bound form.